Thiol_ or thionothiolphosphoric (-phosphonic, -phosphinic) acid esters of chloromethoxy benzotriazole compounds



United States Patent Office 3,242,191 Patented Mar. 22, 1966 3,242,191THIOL- R THIONOTHIOLPHOSPHORIC (-PHOS- PHUNIC, -PHOSPHINIC)ACID ESTERS0F CHLO- ROMETHOXY BENZOTRIAZOLE COMPOUNDS Hugo Malz, Leverkusen, KlausSasse, Cologne-Stammheim, and Giinter Unterstenhofer, Upladen, Germany,assignors to Farbenfahriken Bayer Aktiengesellschaft, Leverkusen,Germany, a German corporation No Drawing. Filed Jan. 23, 1964, Ser. No.339,607 Claims priority, applicatiisn Ggrmany, Jan. 26, 1963,

8 Claims. (01260-308) The present invention relates to and has as itsobjects new and useful, insecticidally and acaricidally activephosphorus containing compounds.

More specifically this invention is concerned with thiolorthionothiol-phosphoric (-phosphonic, -phosphinic) acid esters of thegeneral structure haloalkyl, nitro, alkoxy and/ or alkylmercapto groupsand n is a whole number from 1 to 4. Compounds according to theinvention can be illustrated as follows: R and R stand for lower alkoxyhaving up to 4 carbon atoms; R can stand. for lower alkyl having up to 4carbon atoms and R can stand'for lower alkyl having up to 4 carbon atomsor lower alkoxy having up to 4 carbon atoms; and R and R can stand forethoxy or methoxy, n is 1 or 0 and Y is chlorine, trifluoromethyl,methyl or methoxy.

In accordance with the present invention it has been found thatcompounds of the above composition are obtained in a smoothly proceedingreaction and with good yields by reacting thiolor thionothiolphosphoric(-phosphonic, -phosphinic) acids of the general formula it s Z R2 with1-(halomeithoXy)-benztriazoles of the formula In the last-givenformulae, the symbols R R X, Y and n have the same meaning as indicatedabove, whilst Z stands for a hydrogen atom, a monovalent metalequivalent, preferably an alkali metal or the ammonium group, and Haldenotes a halogen atom.

The reaction according to the invention is preferably carried out in thepresence of inert solvents or diluents. As such agents, aliphatic oraromatic, optionally halogenated hydrocarbons, furthermore alcohols,ketones, ethers or nitriles have proved to be particularly suitable.Furthermore, it is advantageous for achieving good yields and obtainingpure products to allow the process according to the invention to proceedat slightly to moderately elevated temperatures (about 30 to C.) andafter the starting components have been combined to heat the reactionmixture further for some time, whilst stirring, in order to complete thereaction.

Furthermore the reaction according to the present process is preferablycarried out in the presence of acidbinding agents. Alkali metalcarbonates or alcoholates as well as tertiary amines are especiallysuitable as such agents.

Instead of operating in the presence of the abovementioned acid-bindingagents, it is, however, also possible to prepare first the salts,preferably alkali metal or ammonium salts, of the above-mentionedthiolor thionothiolphosphoric (-phosphonic, -phosphinic) acids insubstance and to react these subsequently according to the presentinvention.

The l-(halomethoxy)-benztriazoles required as starting materials for theinventive process have hitherto not been described in the literature.They can, however, be produced by methods known in principle, i.e., byreacting the corresponding l-hydroxy-benztriazoles with formaldehyde andhydrochloric acid and subsequent halogenation of1-(hydroxy-methoxy)-benztriazoles obtained as intermediate products withthe usual halogenating agents, for example thionyl chloride.

Some of the thiolor thionothiol-phosphoric (-phosphonic, -phosphinic)acid esters obtainable according to the present invention are colourlessto slightly yellowcoloured crystalline substances which can readily befurther purified by recrystallisation from the customary solvents. Inpart, however, the compounds are obtained in the form of oils whichcannot be distilled without decomposition.

The inventive products are distinguished by excellent insecticidalproperties and are therefore employed as pest control agents,particularly in plant protection.

The new compounds of the present invention very effectively kill insectslike aphids, spider mites, caterpillars, beetles, flies, ticks, etc.They distinguish themselves especially by a good contact-insecticidalactivity and mostly also by a systemic and ovicidal action. At the sametime they have an activity on eating insects such as caterpillars. Mostsurprisingly they are of remarkable low toxicity against warm-bloodedanimals. They may be used in the same manner as other known phosphoricinsecticides, i.e., in a concentration from about 0.00001% to about 1%,diluted or extended with suitable solid or .liquid carriers or diluents.Examples of such solid carhave been tested against aphids, spider mitesand caterpillars.

Aqueous dilutions of these compounds have been prepared by mixing theactive ingredients with the same amounts of dimethyl formamide as anauxiliary solvent adding thereto 20% by weight referred to activeingredient of a commercial emulsifier consisting of a benzyl hy- Aqueousconcentration (in Killing Compound percent active ingredient/ rate (inwater) percent) (b) Against spider mites: Bean plants (Phaseolusvulgaris) of about 15 inches height are sprayed drip wet with solutionsas prepared above and in a concentration as shown below. The bean plantshave been infested heavily with the two-spotted spider (speciesTetranychus telarius). Evaluation has been carried out after 24 hours,48 hours and 8 days. The following results have been obtained:

Aqueous concentration (in Killing Compound percent active ingredient]rate (in Water) percent) (c) Against caterpillars of the type diamondblack moth (Plutella maculipennis): white cabbage has been sprayed dripwet with aqueous emulsions as prepared above in a concentration as shownbelow. Caterpillars (10 each) have been placed on the sprayed leaves ofthe white cabbage. The living status has been determined after 24 and 48hours.

The following results have been obtained:

Aqueous concentration (in Killing Compound percent active ingredient/rate (in water) percent) The following examples are given for thepurpose of illustrating the invention as claimed:

Example 1 A mixture of g. of l-hydroxy-benztriazole (benzazimidole), 75ml. of 30% formaldehyde, 500 ml. of Water and 5 ml. of concentratedhydrochloric acid is heated at 100 C. for 1 hour. The reaction mixtureis then allowed to cool, the precipitate formed is filtered off withsuction, washed with water and the product dried at 60 to 70 C. underreduced pressure. The yield amounts to 104 g. of 1-(hydroxy-methoxy)-benztriazole which melts at about 160 C. withdecomposition.

48.5 g. of 1-(hydroxy-methoxy)-benztriazole are suspended in 300 ml. ofchloroform. 44 g. of thionyl chloride are added dropwise to thissuspension at room temperature, while cooling it with cold water, themixture is stirred until a clear solution is formed which issubsequently boiled under reflux for another half hour. The solvent isthen distilled oif in a vacuum. As residue, there remain about 50 g. ofl-(chloromethoxy)-benztria zole. The melting point of the substanceafter recrystallising it from dioxan is l71 C. (with decomposition).

A solution or suspension of 18.4 g. of l-(chloro-methoxy)-benztriazoleand 17.5 g. of the ammonium salt of 0,0-dimethylthionothiol-phosphoricacid in ml. of acetone is heated at boiling temperature for about onehour, whilst stirring. The precipitated ammonium chloride issubsequently filtered ofI" with suction at room temperature and thefiltrate evaporated under reduced pressure. There remains a colourlesscrystalline residue which is recrystallised from methanol. 23 g. of thecompound of the above structure are thus obtained in the form ofcolourless crystals which melt at 83 to 84 C.

Analysis.-Calculated for C H O N PS C, 35.4%; H, 3.9%; N, 13.8%; P,10.2%; S, 21.0%. Found: C, 35.0%; H, 4.1%; N, 14.0%; P,9.9%; S, 20.7%.

Caterpillars are destroyed to 70%, aphids and spider mites even to 100%by 0.004% solutions of the product.

Exam ple' 2 A mixture of 27.6 g. of l-(chloromethoxy)-benztriazole, 28.5g. of the ammonium salt of 0,0-diethylthiolphosphoric acid and 200 ml.of acetone is heated at boiling temperature for about 30 minutes. Theprecipitated ammonium chloride is subsequently filtered off with suctionand the filtrate evaporated in a vacuum. After the solid residue hasbeen recrystallised from acetic acid ethyl ester, about 33 g. of theproduct of the above constitution are obtained in the form of colourlesscrystals of melting point 74 to 76 C.

0.004% solutions of the compound destroy spider mites and aphids to100%, caterpillars to 90%.

Example 3 A suspension of 9.5 g. of the ammonium salt of ethyl-O-ethyl-thionothiol-phosphonic acid in 75 ml. of methyl-ethylketone isreacted With 9.2 g. of 1-(chloromethoXy)-benztriazole While stirring.Subsequently the mixture is heated to boiling point for one hour. Theprecipitated ammonium chloride is subsequently filtered off With suctionat room temperature and the filtrate evaporated in a vacuum. Thecrystalline distillation residue is washed with Water and finally driedon a clay plate. There are obtained 10 g. of the compound of the abovestructure in the form of colourless crystals of MP. 75 to 77 C.

Example 6 Aphids and spider mites are completely destroyed, caterpillarsare killed to 60% by 0.01% solutions of the ester.

Example 4 (CH) 1) S 011 O N \N '3 2 2 In the same manner as described inExamples 1 to 3, the following compounds can be obtained: N

Insecticidal activity Administration Concentra- Killing ConstitutionPhysical properties against tion of rate in active percent ingredient Al phids 0.01 100 (CII;O) PS-OII -0 N M.p.85 0 {Spidermites M1 90 Aphids0. 01 100 (oH 2P-so1-n0-N r: Brown on {Spider mites 0'01 O (EH3 llAphids 0. l (CHBO)2PSCHHON {Spider mites 0.1 50

II (OZH50)2P S CHZO N MCI): 106 to 108 APhldS 0.001 100 I 0 Caterplllars0. 01 100 (C2II50)2P S OH2 O N Brown oil Aphids..-" 0.01 100 SpiderElite 0. 01 100 [1 Capt erpillars 0.01 40 (O H O) PSOH O-N N -vdo Aphids0. 01 100 Spider mites 0. 01 100 N 8.2 g. of the potassium salt ofdimethyl-thionothiolphosphinic acid are suspended with 9.2 g. ofl-(chloromethxy)-benztriazole in 150 ml. of methylethylket-one.Subsequently, this suspension is heated to about 50 C. for half an hour.The precipitate formed is filtered off with suction at room temperatureand the filtrate is evaporated in a vacuum. The crystalline distillationresidue is recrystallized from methanol. About 13 g. of the product ofthe above constitution are obtained in the form of colourless crystalsof M.P. of 127 to 128 C.

. We claim:

1. A compound of the formula in which R and R stand for members selectedfrom the group consisting of lower alkyl having up to 4 carbon atoms andlower alkoxy having up to 4 carbon atoms, X stands for a member selectedfrom the group consisting of oxygen and sulphur, Y stands for a memberselected from the group consisting of halogen, lower alkyl having up to4 carbon atoms, halogen substituted lower alkyl having up to 4 carbonatoms and lower alkoXy having up to 4 carbon atoms and in which Itstands for a member selected from the group consisting of zero, 1 and 2.

2. A compound according to claim 1 wherein R and R stand for loweralkoxy having up to 4 carbon atoms.

3. A compounding according to claim 1 wherein R stands for lower alkylhaving up to 4 carbon atoms and R stands for lower alkyl having up to 4carbon atoms or lower alkoxy having up to 4 carbon atoms.

4. A compound according to claim 1 wherein R and R stand for ethoxy ormethoxy, n is one or zero and Y is chlorine, trifluoromethyl, methyl ormethoxy.

5. The compound of the formula 6. The compound of the formula ReferencesCited by the Examiner UNITED STATES PATENTS 2,902,493 9/1959 Lorenz eta1 260308.2

FOREIGN PATENTS 1,176,671 4/ 1959 France.

NICHOLAS S. RIZZO, Primary Examiner.

1. A COMPOUND OF THE FORMULA 